화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.106, No.2, 400-403, 2002
An ab initio study of linear XH-HX hydrogen halide anions
This paper examines the stabilities of singly charged anions with the linear opposed dipole structures: FH-HF, ClH-HCl and BrH-HBr at MP2 and CCSD(T) levels. With 6-311+G(3df,2p) basis sets on Cl and Br and aug-cc-pvdz on H and F, MP2 structures were obtained for all three systems. Since the neutral dimers with opposed dipoles are unstable, the energies for the electron detachment processes were evaluated relative to separated free neutrals, viz.: XH-HX.- --> e(-) + 2HX. At the CCSD(T) level these energies were 0.26 and 0.84 V for HCl and HBr, respectively, but the value for HF is negative. The addition of diffuse orbitals at the central point between the two H atoms lowered the energy and caused the H-H distance in the FH-HF species to increase. Also the excess electron moved into the diffuse orbitals and the species assumed a solvated electron structure, a finding which is in agreement with previous work. In contrast, for the HCl and HBr species the addition of diffuse orbitals had no significant effect. The optimized geometries, charge and spin distributions, and the adiabatic electron detachment energies all remained essentially unchanged. This result and other molecular parameters indicated that in the ClH-HCl and BrH-HBr anions the extra electrons were located in valence orbitals made up from the sigma* orbitals of the two HX molecules. The nature of these orbitals was discussed. Since the dipole moment of the HCl.HCl neutral dimer is considered too small for formation of a dipole-bound anion state (as occurs with HF.HF), it is quite probable that HCl dimer anion observed experimentally is of the XH-HX.- type.